CN110713170B - Hydrogen production method by hydrolysis of borohydride by using water vapor - Google Patents
Hydrogen production method by hydrolysis of borohydride by using water vapor Download PDFInfo
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- CN110713170B CN110713170B CN201910985854.2A CN201910985854A CN110713170B CN 110713170 B CN110713170 B CN 110713170B CN 201910985854 A CN201910985854 A CN 201910985854A CN 110713170 B CN110713170 B CN 110713170B
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- borohydride
- water vapor
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a method for preparing hydrogen by hydrolyzing borohydride with water vapor, which comprises the steps of uniformly mixing borohydride, a catalyst and leavening agent powder, heating water or a water-containing substance, and introducing the generated water vapor into a solid mixture for preparing hydrogen by hydrolyzing. The method utilizes water vapor to supply water, greatly improves the hydrogen storage density, increases the reaction contact area and improves the utilization rate of borohydride; and the reaction rate can be controlled by adjusting the temperature and supply amount of the water vapor. The swelling agent is added into the hydrogen production material, so that the permeability of water vapor is improved, the water vapor is quickly and fully contacted with the solid mixture, the caking phenomenon caused by crystallization of a byproduct metaborate is avoided, and the reaction efficiency of borohydride is effectively improved. The water or the water-containing substance and the solid mixture are separately placed, so that the storage and the transportation are convenient, and the control of the hydrogen production rate is convenient.
Description
Technical Field
The invention relates to a hydrogen production technology, in particular to a method for producing hydrogen by hydrolyzing borohydride with water vapor.
Background
With the rapid development of economy, fossil energy is consumed in large quantities, causing shortage of non-renewable energy and serious environmental pollution. The hydrogen energy can be ideal energy in the future, can provide fuel for a fuel cell, has high energy density of the hydrogen gas and no pollution of products, and effectively solves the problems brought by the existing fossil fuel. There are many methods for producing hydrogen, such as catalytic reforming hydrogen production, biological hydrogen production, photocatalytic hydrolysis hydrogen production, electrolytic water hydrogen production, borohydride hydrolysis hydrogen production, and the like. Among them, hydrogen production by hydrolysis of borohydride is the most widely studied one at present, and industrial large-scale hydrogen production can be realized. The hydrogen prepared by hydrolyzing the borohydride has high purity and controllable hydrogen production rate, can solve the practical problems of storage, transportation and the like of the hydrogen, and provides a convenient and safe solution for the utilization of hydrogen energy.
In the existing hydrogen production schemes by hydrolysis of borohydride, borohydride is mostly prepared into alkaline solution, and then the alkaline solution reacts with a catalyst to produce hydrogen. For example, CN 108238586 a discloses a method for producing hydrogen from sodium borohydride, which comprises preparing sodium borohydride into an alkali solution, preparing an inorganic acid solution, sequentially adding the alkali solution and the acid solution into a hydrogen reactor through two liquid supply pipelines, and adjusting the liquid inlet amount to control the hydrogen production speed. According to the method, sodium borohydride and inorganic acid are respectively prepared into solutions and then are led to a reactor to realize hydrogen production, so that the whole system is complicated; the temperature is difficult to rapidly rise due to the form of double solutions, and the starting speed is slow; the increase in the amount of water lowers the hydrogen storage density of the entire system.
In order to improve the hydrogen storage density, the prior art adopts the technology that all raw materials are solid to produce hydrogen, namely borohydride solid or other hydrogen producing solid is mixed with solid matter containing water, and the mixture is heated to produce hydrogen. For example, CN 104649225 a discloses a portable all-solid hydrogen production material, and a preparation method and an application thereof, which proposes that a solid substance which reacts with water to release hydrogen and a solid substance containing water are fully mixed, and heated to the water-loss temperature of the solid substance containing water to produce hydrogen. The hydrogen production process described in this patent suffers from the following disadvantages: firstly, the water loss temperature of some water-containing compounds is low, the water loss can be lost when the water-containing compounds are heated to 40 ℃, the solid is mixed and needs to be stored in a low-temperature environment, otherwise, hydrogen can be generated at any time to cause danger, meanwhile, the water loss temperature of some compounds is very high, the water loss can be started when the water-containing compounds are heated to hundreds of degrees, the storage and the transportation of the solid mixture are convenient and safe, but the energy consumption in the reaction process is increased. Secondly, all the raw materials are mixed together, so that the speed and the start-stop control in the reaction process are difficult, and hysteresis often exists. And thirdly, in order to fully react the solid mixture, the solid mixture must be uniformly mixed and heated as much as possible, so that the difference of the internal temperature and the external temperature of the mixture is reduced, otherwise, the local caking phenomenon is easy to occur, and the reaction efficiency and the hydrogen yield are seriously influenced due to the limited permeability of crystal water.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing hydrogen by hydrolysis of borohydride by using water vapor, which is characterized in that the water vapor is introduced into a solid mixture of the borohydride, a catalyst and a leavening agent to prepare the hydrogen by hydrolysis.
In order to achieve the purpose, the invention adopts the following specific technical scheme:
a method for preparing hydrogen by hydrolysis of borohydride by using water vapor comprises the following steps:
s1: weighing borohydride, a catalyst and leavening agent powder, and uniformly mixing;
s2: weighing water or water-containing substances for later use;
s3: separately placing the mixed powder and the water/water-containing substance in a reaction vessel;
s4: heating the water/water-containing substance end, introducing the generated water vapor into the tail end of the mixed powder, and collecting the hydrogen generated by the reaction.
Preferably, the mass ratio of the borohydride, the catalyst, the leavening agent and the water or the water-containing substance is 1: (0.5-1): (0.3-0.5): (1-3).
Preferably, the leavening agent is one or more of activated carbon, vermiculite, molecular sieve and foam particles.
Preferably, the borohydride is one or more of sodium borohydride, potassium borohydride, lithium borohydride, magnesium borohydride and calcium borohydride.
Preferably, the catalyst is a solid acid, a strong acid and weak base salt or a mixture of the two. The catalyst promotes the forward reaction, the solid acid is boric acid, and the strong acid weak base salt is anhydrous magnesium sulfate or anhydrous zinc sulfate.
Preferably, the water-containing substance is sodium carbonate decahydrate, a water-absorbing molecular sieve or water-absorbing vermiculite.
Further, the heating temperature of the water-containing substance is 80-150 ℃.
The method comprises the steps of uniformly mixing borohydride, a catalyst and leavening agent powder, heating water or a water-containing substance, and introducing generated water vapor into a solid mixture to hydrolyze and produce hydrogen. The water or water-containing substance and the solid mixture are separately placed, water is supplied by using water vapor, the storage and the transportation are convenient, the hydrogen storage density is effectively improved, compared with the direct mixed reaction of all solid raw materials, the contact area between the raw materials is greatly increased, the utilization rate of sodium borohydride is improved, and the reaction rate can be controlled by adjusting the temperature and the supply quantity of the water vapor in the reaction process. More specifically, the reaction efficiency of water vapor and a solid mixture is optimized by adding a leavening agent, the leavening agent can increase the gaps among the mixed powder particles, on one hand, the resistance of the water vapor entering the solid mixture can be reduced, so that the water vapor fully permeates into the solid mixture, and the hydrogen production reaction can be rapidly and comprehensively generated; on the other hand, the leavening agent can maintain the looseness of the solid mixture to a certain degree in the reaction process, and the impact force exerted by the water vapor on the solid mixture can prevent the effective byproduct metaborate from being condensed on the surface of the solid borohydride in a large quantity, so that the reaction efficiency is improved; in addition, the leavening agent has good thermal conductivity, and ensures that the inside of the solid mixture is heated uniformly. More optimally, the reaction efficiency is further improved by strictly controlling the proportion of each raw material, and the weight ratio of the weighed water or water-containing substance, the hydroboron, the catalyst and the leavening agent is 1: 1/2-1: 1-3: 1/3-1/2. In addition, the invention selects sodium carbonate decahydrate, water-absorbing molecular sieve or water-absorbing vermiculite as water-containing substances, the water-containing substances can lose crystal water by controlling the heating temperature to be 80-150 ℃, and the safety and the storage convenience of the water-containing substances are improved by selecting the water-containing substances with proper water-losing temperature.
The invention has the following beneficial effects:
the solid mixture of water vapor, borohydride, a catalyst and a leavening agent is used for reaction, so that the hydrogen storage density is greatly improved, the reaction contact area is increased, and the borohydride utilization rate is improved; and the reaction rate can be controlled by adjusting the temperature and supply amount of the water vapor.
The swelling agent is added into the hydrogen production material, so that the permeability of water vapor is improved, the water vapor is quickly and fully contacted with the inside of the solid mixture, the caking phenomenon caused by crystallization of a byproduct metaborate is avoided, and the reaction efficiency of borohydride is effectively improved.
The solid borohydride, the catalyst and the leavening agent are mixed, and water or water-containing substances are independently placed, so that the storage and the transportation are convenient, and the control of the hydrogen production rate is convenient.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Weighing 2g of sodium borohydride and 1g of boric acid, adding the sodium borohydride and the boric acid into a mortar, grinding and mixing uniformly, and adding 0.8g of foam particles in a dispersing way; 4g of water is taken and placed at the bottom of the test tube, and a support structure is designed to place a material layer at the upper end of the water surface. The tube was heated to 100 ℃ and the hydrogen produced was collected by draining, producing 4.2L of hydrogen in 60min, 88.6% of the theoretical hydrogen production.
Example 2
Weighing 2g of sodium borohydride and 2g of anhydrous magnesium sulfate, adding the sodium borohydride and the anhydrous magnesium sulfate into a mortar, grinding and mixing uniformly, and dispersing and adding 1g of activated carbon powder; 6g of sodium carbonate decahydrate is placed at the bottom of the test tube, and a support structure is designed to place a material layer at the upper end of the water surface. The tube was heated to 95 ℃ and the hydrogen produced was collected by draining, producing 4L of hydrogen in 60min, 84.4% of the theoretical hydrogen production.
Example 3
Weighing 1g of sodium borohydride, 1g of potassium borohydride and 2g of boric acid, adding the sodium borohydride, the potassium borohydride and the boric acid into a mortar, grinding and mixing uniformly, and adding 1g of activated carbon powder in a dispersing way; 4g of water is taken and placed at the bottom of the test tube, and a support structure is designed to place a material layer at the upper end of the water surface. The tube was heated to 100 ℃ and the hydrogen produced was collected by draining, producing 3.7L of hydrogen in 60min, 91.8% of the theoretical hydrogen production.
Example 4
Weighing 2g of sodium borohydride and 1g of boric acid, adding the sodium borohydride and the boric acid into a mortar, grinding and mixing uniformly, and adding 0.8g of vermiculite in a dispersing way; 6g of water-absorbing vermiculite is placed at the bottom of the test tube, and a support structure is designed to place a material layer at the upper end of the water surface. The tube was heated to 100 ℃ and the hydrogen produced was collected by draining, producing 4.2L of hydrogen in 60min, 88.6% of the theoretical hydrogen production.
Example 5
Weighing 2g of sodium borohydride and 2g of boric acid, adding the sodium borohydride and the boric acid into a mortar, grinding and mixing uniformly, and adding 1g of activated carbon powder in a dispersing way; 6g of the water-absorbing molecular sieve is placed at the bottom of the test tube, and a support structure is designed to place the material layer at the upper end of the water surface. The tube was heated to 100 ℃ and the hydrogen produced was collected by draining, producing 4.3L of hydrogen in 60min, 90.7% of the theoretical hydrogen production.
This detailed description is to be construed as illustrative only and is not limiting, since modifications will occur to those skilled in the art upon reading the preceding specification, and it is intended to be protected by the following claims.
Claims (4)
1. A method for preparing hydrogen by hydrolysis of borohydride by using water vapor is characterized by comprising the following steps:
s1: weighing borohydride, a catalyst and leavening agent powder, and uniformly mixing; the leavening agent is one or more of activated carbon, vermiculite, molecular sieve and foam particles; the catalyst is solid acid, strong acid and weak base salt or a mixture of the solid acid and the strong acid and the weak base salt;
s2: weighing water or water-containing substances for later use; the mass ratio of the borohydride, the catalyst, the raising agent and the water or the water-containing substance is 1: (0.5-1): (0.3-0.5): (1-3);
s3: separately placing the mixed powder and the water/water-containing substance in a reaction vessel;
s4: heating the water/water-containing substance end, introducing the generated water vapor into the tail end of the mixed powder, and collecting the hydrogen generated by the reaction.
2. The method for producing hydrogen by hydrolysis of borohydride with water vapor according to claim 1, wherein the method comprises: the borohydride is one or more of sodium borohydride, potassium borohydride, lithium borohydride, magnesium borohydride and calcium borohydride.
3. The method for producing hydrogen by hydrolysis of borohydride with water vapor according to claim 1, wherein the method comprises: the water-containing substance is sodium carbonate decahydrate, water-absorbing molecular sieve or water-absorbing vermiculite.
4. The method for producing hydrogen by hydrolysis of borohydride with water vapor according to claim 3, wherein the method comprises: the heating temperature of the water-containing substance is 80-150 ℃.
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| CA3123117A1 (en) * | 2018-12-21 | 2020-06-25 | Hydrogen In Motion Inc. (H2M) | Method for generating hydrogen from a nitrogen containing borane compound and active metal borohydride mixture |
| CN111348621B (en) * | 2020-04-21 | 2021-09-24 | 杭州氢源素生物科技有限公司 | Hydrolysable hydrogen production material using hydrogen-containing compound |
| CN111514032B (en) * | 2020-04-21 | 2022-10-18 | 杭州氢源素生物科技有限公司 | Sandwich mask capable of producing hydrogen, generating heat and preserving heat |
| CN111777037B (en) * | 2020-06-19 | 2023-05-26 | 浙江高成绿能科技有限公司 | Fuel for hydrogen production by adding water and preparation process thereof |
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| ITRM20030315A1 (en) * | 2003-06-25 | 2004-12-26 | Francesco Massimo De | MAGNETIC BORDERED DEVICE FOR THE GENERATION OF HYDROGEN FROM ALKALINE BOROHYDRIDE. |
| CN101428756A (en) * | 2008-11-27 | 2009-05-13 | 中山大学 | Automatic hydrogen production method by using hydroboron composition |
| CN101841048B (en) * | 2010-02-26 | 2012-09-26 | 中国科学院上海微系统与信息技术研究所 | Method for generating hydrogen through lithium borohydride-porous carbon hydrolysis and reaction system |
| CN104787721A (en) * | 2015-04-15 | 2015-07-22 | 成都瑞顶特科技实业有限公司 | Hydrolysis hydrogen production agent |
| WO2017127022A1 (en) * | 2016-01-18 | 2017-07-27 | Advanced Material Engineering Pte. Ltd. | Portable hydrogen generator |
| CN106495095B (en) * | 2016-11-02 | 2018-08-03 | 北京明德清源科技开发有限公司 | A kind of composite hydrolysis hydrogen manufacturing material and hydrogen production process |
| CN106495096B (en) * | 2016-11-02 | 2018-08-03 | 北京明德清源科技开发有限公司 | A kind of solid hydrolysis hydrogen manufacturing material |
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